Disinfectants



2,978,465 V i atented-A r,-

DISINFECTANTS Dietrich Jerchel, Mainz, Germany, 'assignor to C. H. Boehringer Sohn, Ingelheim (Rhine), Germany, a partnership of Germany No Drawing. Filed May 21, 1958, Self. No. 736,665 Claims priority, application Germany May 28, 1957 6 Claims. (Cl. 260-A04) -The present invention relates to disinfectants, and more particularly to germicidal acylated aminophenols and to compositions comprising such germicidal agents.

I have found that acylated aminophenols having the structural formula wherein R is alkenyl with to 20 carbon atoms and from 1 to 3 olefinic bonds, X is chlorine or bromine, n is an integer from 1 to 3, inclusive, and Y is hydrogen, chlorine or bromine, are powerful germicidal agents, and that compositions having said acylated aminophenols incorporated therein posses excellent disinfectant properties.

The novel compounds according to the present invention are soluble in water and have properties similar to soap. In other words, they form foaming solutions and may therefore be combined with other soaps without detriment to the characteristicetfectsof either soapy com ponent.

The presence of olefinic bonds'in the fatty acid moiety of acylated 'aminophenols is of considerable importance to their germicidal activity. Thus, saturationof the olefinic bonds leads to a substantial loss in germicidal activity, as illustrated by the following table:

TABLE t, Growth 0; Growth of Staph- Coliform Acylated Aminophenol Dilution ylococcua Bacteria Aureus Undecylenic acid-2-hydroxy-5- {1:2, 100,000

chloro-anllide 1: 5, 100, 000' 1251,000 Sorbic acld-2-hydroxy-5-chloro- 1:110,000

anilide 1345,000 x 1:81,000 r 2 Y 1121,0110 a Undecylic acid-Z-hydroxy-G 1 m' i -r 121100 .1:5, 10o t In the above table w indicates that no bacteria growth was observed;

+' indicates that definite bacteria growth was observed;

(+) indicates that an insignificant amount of bacteria growth was'observed.

Evaluation of the, values tabulated above clearly shows that very dilute solutionscontaining as rlittle -as 1 part per 2 million of an acylated aminophenolhaving double 2 decylic acid anilide with respectito coliform bacteria is also evident from the tabulated values. p

The acylated aminophenols according to the present invention may be incorporated into body powders, after I I shave lotions, bath water additives, cleansing agents for use in dairies, hospitals and the like, dish-rinsing compositions and all other compositions and solutions intended I for-use in suppressing the growth and propagation of w I bacteria, in concentrations between 0.1 and 8.0% by weight, and preferably 1 to 3% by weight. l

The following examples are given to illustrate various germicidal compositions containing the acylated aminophenols according to the present invention which may be compounded:

Example I V BODY POWDERS Gm: Starch ZOQ Zinc oxide 'Y Talcum Magnesium carbonate 20 Titanium oxide 20 Acylated aminophenol 10 B Talcum 340 Kaolin 60 Zinc oxide 7 p 100 Magnesium carbonate 10 Titanium oxide '20 Acylated aminophenol 10 t Example [I AFTER-SHAVE LOTION j I K Gm. Water 750 I Alcohol r 250 Menthol 1.5 Lemon oil 2.0 Orange oil 1.0 Neroli oil 0.5 Lavender oil 0.5 Acylated aminophenol 10.0 f

' Example III 1 DIsH-rtr sI G COMPOSITION Trisodium-phosphate Q...'J *6Q Tetrasodium pyrophosphate V30 Alcohol sulfonate 5f" Acylated aminophenol ,5 Example IV )7 1 CLEANSING COMPOSITION ort USE I nAmIns Gm; Soda ',45, vTrisodium phosphate -f35 Sodium silicate j I i '10 Qaustic soda 7 Q5; Acylated aminophenol ,L 1 .5 In Examples I through"IVjabove'-the term acylat'edu aminophenol is intended to mean any 'aciylated ianiino} phenol containing at least one olefinic' bond in efatty bonds in'the fatty acid moiety are effective ininhibitingf greater germicidal" activity of sorbic acid-.Z-hydroxy- 5'-chloro-ani1ide"as comparedto the corresponding'iunto I v s a v, The olefinic acylated aminophenol! accord ng present invention are advantageously produced by the grow th lof Staphylococcus aureugf'whereasfmuchless "dilute solutions of an acylated aminophenol havingonlysaturated-bonds "in the fatty acid moiety are inefi ctive.

'acid moiety and havin the' structuial foririula ilefincd above. In addition to the acylated aminophenols acco ing to the present inventiong jother germici 0f course also be included in the composit in Examples Ito IV, if desired; 1

ing an olefinic acid chloride with a halogenated aminophenol, as illustrated by the following examples:

Example V UNDECYLENIC ACID-2-HYDROXY-5-CHLORO-ANIL1DE II l 4.7 gm. undecylenic acid chloride and 12.2 gm. 2- amino-4-chlorophenol were dissolved in dioxan, and the solution was heated for 4 hours at 35-40 C. accompanied by stirring. The reaction mixture was then allowed to stand overnight, whereupon the solvent was removed by vacuum distillation. The distillation residue was washed several times with 2 N hydrochloric acid and was then recrystallized from alcohol in the presence of animal charcoal. Colorless crystals having a melting point of 80-81" C. were obtained. The yield was 5.5 gm., which corresponds to 76.6% of the theoretical yield. C H ClNO .Calculated: C, 65.89; H, 7.81; N, 4.52%. Found: C, 66.02; H, 7.94; N, 4.86%.

Example VI SORBIC AClD-2-HYDROXY-5-CHLORO-ANILIDE By a procedure analogous to that described in Example V 2.0 gm. sorbic acid-2-hydroxy-5-chloro-anilide were obtained aromas sorbic acid chloride and 4.7 gm. 2-arnino-4-chlor'ophenol. The yield corresponded to 50% of the theoretical yield. The product was a colorless crystalline substance having a melting point of 172- 173 C.

Example VII UNDECYLENIC ACID-2-HYDROXY-3,5-DICHLORO- ANILIDE HO Cl CHz=CH-(CHM- 7 Following the procedure described in Example V, undecylenic acid-2-hydroxy-3,S-dichloro-anilide was obtained from undecylenic acid chloride and 2-arnino-4,6- dichlorophenol. V V p 7 Example VIII 7 UNDECYLENIC ACID-2-HYDROXY-3,4,5,6-TETRACHLORO- ANILIDE H 4.5 gm. undecylenic acid chloride were added dropwise to a solution of 12.7 gm. 2-amino-3,4,5,6-tetrachlorophenol in dioxan under anhydrous conditions. The resulting mixture was allowed to stand overnight and was then heated for 6 hours at 40-45 C. accompanied by stirring. Thereafter, the dioxan solvent was removed by vacuum distillation and the residue was recrystallized several times from ethanol in the presence of animal charcoal. The recrystallized product was obtained in the form of colorless needles having a melting pointo'r' 108 109", C.g The yield was 7.4 gm., which corresponds 'to 73% of the theoretical yield. 1 a C H C1 NO Calculated: C, 49.72; H, 5.12; N, 3.39%. Found: C, 49.56; H, 5.13;.N, 3.67%.

4 Example IX DODECYLENIC acrn-n a-nrnaoxr-s-cnnono- ANILIDE c1 onr=cnom g-t -r 6 gm. dodecylenic acid chloride were added dropwise, at room temperature, to a mixture of 4 gm. 4-chloro-2- aminophenol, cc. anhydrous ether, 50 cc. dioxan and 2.5 cc. pyridine, accompanied by vigorous mechanical stirring. The resulting mixture was allowed to stand overnight and was then stirred for an additional six hours at 40 C. on a water bath. Thereafter, the ether was removed by vacuum distillation and the residue was treated with warm 2 N hydrochloric acid to remove the pyridine-chlorohydrate formed by the reaction. The resulting mixture was then filtered and the filter cake was recrystallized from ethanol. The yield was 3.1 gm. The crystalline product had a melting point of 88-90 C.

Example X UNDECY LEN IC ACID-2-HYDROXY-5 -BROMO-ANILIDE 4.7 gm. undecylenic acid chloride and 15 gm. 2-amino- 4-bromophenol were dissolved in dioxan, and the solution was heated for 4 hours at 35-40 C. accompanied by stirring. The reaction mixture was then allowed to stand overnight, whereupon the solvent was removed by vacuum distillation. The distillation residue was washed wherein R is alkenyl with 5 to 20 carbon atoms having from 1 to 3 olefinic double bonds, X is selected from chlorine and bromine, n is an integer from 1 to 3, inclu' sive, and Y is selected from the group consisting of hydrogen, chlorine and bromine.

2. Undecylenic acid-2-hydroxy-S-chloro-anilide.

3. Sorbic acid-Z-hydroxy-S-chloro-anilide.

4. Undecylenic acid-2-hydroxy-3,S-dichloro-anilide.

5. Undecylenic acid-2-hydroxy-3,4,5,6-tetrachloro-anilide.

6. Dodecylenic acid-A"-2-hydroxy-S-chloro-anilide..

References Cited in the file of this patent UNITED STATES PATENTS samba; rev. 2s. 19: 

1. ACYLATED AMINOPHENOLS HAVING THE STRUCTURAL FORMULA 